DE2017974A1 - Process for the preparation of aminoalkylenephosphonic acids - Google Patents

Description

Jloh. A. Benckteer & nbH - £ 7OO Lucfwifishafen / Rhine

Fwnruf (062O "59031 Account number 0464872 Wire address Bencki «* r Ludwigahaf« nrh * ln

Ludwigshafen, 7.4.1970 Dr B / Mm - int.Nr.

Process for the preparation of aminoalkylenephosphonic acids

The present invention relates to a process for the preparation of aminoalkylenephosphonic acids.

The aminoalkylenephosphonic are excellent complexing like ner of polyvalent metals ,. eg calcium, magnesium, iron etc. They are resistant to hydrolysis and are therefore mainly added to liquid cleaning agents. Since the aminoalkylenephosphonic, crowds so-called vaccine already in bottom ¹ chiometrischen quantities act, si · have gained increasing importance in recent years.

A number of processes are already known for producing the compounds. So are the connections according to the Germans Auslegeschrift 1 214 229 made from aline, formaldehyde and phosphorous acid. In this implementation, however, always arises a mixture of different components, so that in the ^

German Auslegeschrift 1 259 .337 is proposed a ™ To use excess phosphorous acid in order to obtain purer products.

In British patent specification 1,142,294, a process is also described in which, instead of phosphorous acid, the cheaper phosphorus trichloride is reacted with anine and formaldehyde to form aminoalkylenephosphonic acids.

_ 2 - ORIGINAL BATHROOM

109845/1891

Joti. A. Bencki & ev Gmhiri * β70θ

ifisltafen / FIiiein

Foat compartment 21O1S7 2017974

Telephone COSZI) "59631 F «tnichr« r

- 65O -

DrahtansefciriifC: E ~ .-: cJii «er Ludwigahafenrhetn

A disadvantage of this process has been shown to be that the reaction runs very stormy. Since the reaction solution is strong heated, the phosphorus trichloride can only slowly and under good Cooling are added dropwise. Due to the low boiling point of phosphorus trichloride, however, it is often unavoidable that some of the phosphorus trichloride is distilled off or is entrained by the hydrogen chloride gases escaping in large quantities. This phosphorus trichloride is then missing in the implementation, which results in a reduction in yield, unless one works with an excess of phosphorus trichloride to compensate for the loss.

It has now been found that these disadvantages can be prevented if, instead of phosphorus trichloride, glycol chlorophosphites with aldehydes or ketones and amines or salts are used Amines or acid amides of lower mono- or dicarboxylic acids.

Compared to the known method of phosphorus trichloride, the method of the invention has the advantage that the glycol chlorophosphites have a significantly higher boiling point than phosphorus trichloride and can therefore be added much more quickly without the risk of loss of glycol chlorine by heating the reaction solution -phoephite occur by distilling off. For example, boiling Äthylenglykolchlor phosphite la vacuum at 50 mm pressure at 71 ° C while phosphorus trichloride passes already under normal pressure at almost the same temperature, namely at 74.5 ⁰ C. The procedure of

₃ _ BAD ORIG'NÄL

109845/1898

uofVAuBenckteerGnnttri · 6700 Luriwigshafen / Rheln

P.O. Box 21 01 67 C U / 9 / A

Telephon (0621) "59031> __ Telegraph 046487?

Wire address Benckiter Ludwigehafenrhein

Finding is particularly advantageous when making larger ones Amounts of aminoalkylenephosphonic acids, since factors such as cooling and reaction time are decisive for the economic viability of the process.

Processes are already known according to which phosphorous acid diesters are reacted from lower monohydric alcohols with amine and formaldehyde. Here, however, the esters are used first of the aminoalkylenephosphonic acids which only become the acids nuts are saponified. According to the invention, on the other hand, chloroglycol phosphorous acid esters are used, and during the reaction Hydrogen chloride is formed, which has a favorable influence on the conversion and also saponifies the glycol ester at the same time, so that nan immediately arrives at the free aminoalkylenephosphonic acids. In addition, the chlorophosphorous acid esters used according to the invention can also be obtained from polyhydric alcohols Produce better and purer than the well-known phosphorous acid diesters of monohydric alcohols. This is how the implementation of 1 mole of Phosphortrichlorld alters 2 moles of monohydric alcohol Mixtures of phosphorous acid diesters and ester halides, which first have to be purified while the reaction is taking place The glycol chlorophosphoric acid ester forms almost quantitatively from 1 hol Phoephortrlchlorid with 1 mol glycol. It is therefore possible to use the crude Glykolchlorphosphorigsäureester without Purification to be implemented directly with AedLn and formaldehyde to form the aminoalkylenephosphonic acids, which is a further advantage of the process according to the invention over the known processes represents.

As glycol-chlorophosphites, for example, 1,2-ethylene

BAD ORIGINAL 10984 5/1898

Joh.A.Benckfeer ümbH > «7OO Luriwigshafen / Rhine P.O. Box 21 01 67 t U I / 9 /

Telephon (0621) "59031 Telegraph 04 6487? Wire address Benckieer Ludwigehafanrheln

glycol-chloro-phosphite _r 1, 2-propylene glycol-chloro-phosphite, 1, 3-butylene glycol-chloro-phosphite used.

The glycol-chlorophosphites can be mixed with all the mono- or polyamines or their salts as well as aldehydes and ketones are implemented, which are already from the production process of Amlnoalkylenphosphonsäuren with phosphorous acid or phosphorus trichloride are known.

It has been shown that particularly good yields of aminoalkylenephosphonic acids also in the reaction of glycol-chlorophosphite with acid araids of lower mono- or dicarboxylic acids such as formamide, Oxamide or urea can be obtained.

The reaction can be carried out in various ways. The amine can be mixed with dilute hydrochloric acid in a reaction flask neutralize, add aldehyde and glycol-chlorophosphite and then in a boiling water bath for 1 to 2 hours continue heating. You can also use the free amine with, for example, formalin solution mixed with glycol-chlorophosphite to react.

You can continue to work in a different order by first reacting the glycol-chlorophosphite with the aldehyde and then the amine or a salt of the amine or an acid amide is added.

The glycol-chlorophosphite is made according to known methods Glycol and phosphorus trichloride in the presence of methylene chloride

1098 k 5/1898

Joti. A.BenckteerÜmbH »67OO Luriwlgshafen / Rhein

P.O. Box 21 01 67 20179/4

Telephone (0821) ~ 59031 - 65Ο - Telegraph M 8481?

Wire address Bendciaer Ludwigahafenrheln

obtained as a diluent. After distilling off the diluent on the water bath, the glycol-chlorophosphite becomes distilled in vacuo.

But you can also work without a diluent and use the raw React the ester directly. It is thus possible in one go by adding the aldehyde or ketone to the crude ester and then adding dropwise the Arainchlorhydrat or acid amide to arrive at the aminoalkylenephosphonic acids.

Mixtures of different amines can of course also be used Aldehydes or ketones and glycol-chlorophosphites for implementation to be brought.

The isolation of the reaction products can be carried out in such a way that the reaction solution is concentrated and the crystallized compound by removing and washing with a little water, alcohol or Acetone pure isolated. But you can also use the crude reaction solutions, preferably in the case of phosphonic acids, which crystallize poorly or as oils, direct cleaning agents in solid and incorporate them in liquid form or in aqueous systems use for stone prevention in substoichiometric amounts. The glycol present in the reaction solution does not interfere with this. Rather, the presence of glycol in stone-preventing preparations has proven to be an advantage.

109845/1898

Joh. A.Bencki <) erämbh - β7θθ Lurtwiashafen / Rlieln _ P «» Stfad3 21 01 67 Z U I / Η /

Telephon ίΟ621) "59031 - 650 - Telegraph 0464872

Wire address .tknckieer Ludwigehafenrheln

example 1

To the mixture of 30 g of ethylenediamine VX / 2 mol), 100 g of conc. Hydrochloric acid (1 mol) and 200 g of 30% strength formaldehyde solution (Z mol) are added to a standing water bath within 30 minutes with 252 g of ethylene glycol chlorophosphite (2 mol) while stirring. The temperature of the Reaktioraslösung rises to 80 ⁰ C. The mixture is then further heated for 2 hours in the boiling water bath and then says in vacuo. After washing with water and alcohol, ethylendlaffin-fcetra-toetBylenephosphonic acid) is obtained as a white solid substance.

Yield: 53% of theory.
Example 2

A mixture of 30 g of ethylenediamine (1/2 mol), 100 g conc. Hydrochloric acid (1 mol) and 2OO g of 30-tiger formalin solution (2 mol) and, with stirring, 2SO g of 1,2-propylene glycol chlorophosphite (2 mol) were added dropwise and the mixture was stirred at 110 ° C. for a further 2 hours. The reaction solution can be used directly without purification Detergents are added.

Example 3

To 378 g of ethylene glycol chlorophosphite (raw, not distilled) (3 mol) are stirred with 3OO g of 30% formalin solution (3 mol) placed in standing water bath within 10 minutes. The temperature of the reaction solution rises to 60 ° C. during this process. Afterward 45 g of formamide (1 mol) are added and the The reaction solution was stirred in a boiling water bath for a further 2 hours.

109 «4rSV1898

β7θθ Luriwigshafen / Rheln

P.O. Box 21 01 67

Telephon (0621) "59031 _ CKQ _ Telegraph 0464872

Wire address Bencklaer Ludwlgthafenrheln

On cooling, nitrilo-tris (methylenephosphonic acid) crystallizes the end. It is filtered off with suction and washed with acetone.

Yield: 83% of theory. Example 4 |

To 103 g of diethylenetriamine (1 mol), 500 g of 30% strength formalin solution (CS mol) are added with stirring and then 63O g Ethylene glycol chlorophosphite (5th mol) in a standing water bath dripped. The temperature of the reaction solution rises 85 ° C. The reaction mixture is heated in a boiling water bath for a further 1 to 2 hours. The thus obtained aqueous solution of Dläthylenetriamine-penta- (methylenephosphonic acid) can be used without Cleaning agents can be added directly to cleaning agents.

Example 5 To a mixture of 1Ο3 g diethylenetriamine (1 mol), 300 g %

conc. Hydrochloric acid (3 mol) and 500 g of 30% formalin solution

(5th mol) 770 g 1,3-butylene glycol chlorophosphite (5th mol) added dropwise and the reaction mixture then a further 2 hours heated to 100 to 110 ^{° C.} The aqueous solution thus obtained cleaning agents can be added directly without cleaning.

Example 6

To a mixture of 53.5 g ammonium chloride (1 mol) and 300 g 30% formalin solution (3 mol) are added dropwise with stirring and cooling in a water bath, 378 g of ethylene glycol chlorophosphite (3rd mol)

1098 ⁸ 45/1696

Joh. A. Bencki ^ eh ümbH > 67OO LucOvbrjshafenSRheln _

P.O. Box 21 01 67 if U I / J? / 4

Telephon (0621) "59031 - 650 - Telegraph 04 6487?

Wire address Bencklser Ludwigshafenrheln

and the reaction mixture for 1 to 2 hours in a boiling water bath touched. Nitrilo-tris- (roethylenephosphonic acid) crystallizes on cooling the end. It is filtered off with suction and washed with acetone.

Yield: 71.4% of theory.

109845/1898

Claims (3)

Joh. A. Benckteer timbln · 67OO Luriwigshafen / Rheln / Ul / 9/4 P.O. Box 21 or 67 Telephon (0821) "59031 - O SO - Telegraph 04 6487? Wire address Bencklser Ludwigahafenrheln Claims Process for the production of aminoalkylenephosphonic acids, characterized in that one glycol-chlorophosphites with aldehydes or ketones and amines' or salts of amines or Acid amides of lower mono- or dicarboxylic acids implemented. 2. The method according to claim 1, characterized in that one as glycol chlorophosphite, ethylene glycol chlorophosphite, 1,2-propylene glycol chlorophosphite or 1,3-butylene glycol chlorophosphite begins. 3. The method according to claim 1 to 2, characterized in that that formamide, oxamide or urea are used as acid amides. 109845/1898